Cellulosic product

ABSTRACT

The present invention relates to a process of producing a cellulosic product comprising (i) providing an aqueous suspension of cellulosic fibers, (ii) adding microfibrillar polysaccharide, (iii) adding thermoplastic microspheres, (iv) dewatering the suspension and forming a cellulosic product. The invention also relates to a process of producing a single layer cellulosic product comprising (i) providing an aqueous suspension of cellulosic fibers, (ii) adding microfibrillar polysaccharide derived from softwood and/or hardwood and optionally adding thermoplastic microspheres to the suspension, (iii) dewatering the suspension and forming a cellulosic product. The invention further relates to a cellulosic product obtainable from said processes. The invention also relates to a composition comprising microfibrillar polysaccharide and thermoplastic microspheres and the use thereof.

The present invention relates to a process of producing a cellulosicproduct, such as a single layer cellulosic product and a compositionsuitable for addition to a cellulosic suspension. The invention alsorelates to a cellulosic product obtainable by the process, and the useof said cellulosic product.

BACKGROUND OF THE INVENTION

Today, the development within the papermaking industry is focused onreducing the grammage of cellulosic products such as board productswhile increasing or substantially maintaining their further propertiesincluding strength properties.

WO 00/14333 relates to a method in which latex is used as a binder inthe bulk layer to improve strength properties. However, WO 00/14333suffers from high amounts of chemicals needed as well as problemsrelated to the application of the latex binder. As an example, if latexis added to the wet end, retention problems of the latex on the fibersmay cause deposit problems as well as disturbance of the wet endchemistry balance. Application problems may also occur if latex wereadded to already formed paper or board layers using existing equipment.Latex may also result in repulpability problems.

U.S. Pat. No. 6,902,649 discloses a seed-based enhanced fiber additive(EFA) derived from non-wood which may be used in papermaking. U.S. Pat.No. 6,902,649 states that EFA used as a fiber replacement material canmaintain or increase paper strength properties in applications wherebythe basis weight of the paper is decreased.

One object of the instant invention is to provide a new process ofproducing a cellulosic product, especially a single layer cellulosicproduct, substantially maintaining and/or increasing its propertiesincluding strength properties such as tensile strength while using asmaller quantity of cellulosic material so as to reduce the grammage ofthe formed cellulosic sheets. Yet a further object of the invention isto provide a cellulosic product, especially a single layer cellulosicproduct, in which at least one property of the cellulosic productincluding tensile strength, Z-strength, and/or other strength isimproved or substantially maintained while the bending resistance can besubstantially maintained or increased. A further object of the instantinvention is to provide a composition which may be used as a premix toprovide such cellulosic product.

The Invention

The present invention relates to a process of producing a cellulosicproduct comprising (i) providing an aqueous suspension of cellulosicfibers, (ii) adding microfibrillar polysaccharide, (iii) addingthermoplastic microspheres, and (iv) dewatering the suspension andforming a cellulosic product.

The present invention also relates to a process of producing a singlelayer cellulosic product comprising (i) providing an aqueous suspensionof cellulosic fibers, (ii) adding microfibrillar polysaccharide derivedfrom softwood and/or hardwood and optionally adding thermoplasticmicrospheres to the suspension (iii) dewatering the suspension andforming a single layer cellulosic product.

The term “cellulosic product”, as used herein, includes inter alia pulpbales and cellulosic products in sheet and web form such as paper,paperboard, and board. The cellulosic product may comprise one orseveral layers containing cellulosic fibers.

The term “cellulosic product” as used herein, includes e.g. paperboardcomprising cellulosic fibers and solid board, e.g. solid bleachedsulfate board (SBS) including boards (composed of one or several layersof bleached chemical pulp) coated on the top and optionally on thebackside; solid unbleached sulfate board (SUS) and solid unbleachedboard (SUB) which may be made from unbleached chemical pulp (oftencoated on the top and sometimes on the backside which can be composed ofseveral layers of unbleached chemical pulp in the board); carton board,e.g. folding boxboard (FBB) which may be made with a middle layer ofmechanical pulp between layers of bleached or unbleached chemical pulp(usually coated on the top side and being a low density board with highbending stiffness), folding carton board, liquid packaging board (LPB)including aseptic, non-aseptic packaging and retortable boards; whitelined chipboard (WLC) (which may comprise middle layers of differenttypes of recycled fibers and a top layer usually made from chemicalpulp); fluting and corrugated fluting, unbleached kraftboard, greychipboard and recycled board; liner, liner board and container board,cup board, fully bleached or unbleached kraftliner, testliner,unbleached kraftliner, unbleached testliner and recycled liner such asOCC, White Top Liner consisting of a back layer made from unbleachedchemical pulp or brown recycled fibers and a top layer made frombleached chemical pulp, sometimes including filler such as GCC and PCC;Gypsum board, Core board, Solid fiber board, the inner layers thereofusually consisting of recycled fibers and the outer layers of paper withhigh tensile strength; sack paper, and wrapping paper.

According to one embodiment, the invention provides a cellulosic productsuch as single layer cellulosic product comprising microfibrillarpolysaccharide and optionally thermoplastic microspheres distributedthroughout the cellulosic product, e.g. substantially uniformlydistributed throughout the cellulosic product. According to oneembodiment, the single layer cellulosic product may be coated orlaminated with any number of non-cellulosic coating or layer, e.g.polymer films, metallized films, barrier layers as further disclosedherein.

By the term “microfibrillar polysaccharide” is meant to include speciesderived from polysaccharide without limitation including cellulose,hemicellulose, chitin, chitosan, guar gum, pectin, alginate, agar,xanthan, starch, amylose, amylopectin, alternan, gellan, mutan, dextran,pullulan, fructan, locust bean gum, carrageenan, glycogen,glycosaminoglycans, murein, bacterial capsular polysaccharides, andderivatives thereof.

According to one embodiment, the microfibrillar polysaccharide ismicrofibrillar cellulose which would be the most commonly selectedmicrofibrillar polysaccharide and will therefore be described more indetail herein. Sources of cellulose for the preparation ofmicrofibrillar cellulose include the following: (a) wood fibers, e.g.derived from hardwood and softwood, such as from chemical pulps,mechanical pulps, thermal mechanical pulps, chemical-thermal mechanicalpulps, recycled fibers, (b) seed fibers, such as from cotton; (c) seedhull fiber, such as from soybean hulls, pea hulls, corn hulls; (d) bastfibers, such as from flax, hemp, jute, ramie, kenaf, (e) leaf fibers,such as from manila hemp, sisal hemp; (f) stalk or straw fibers, such asfrom bagasse, corn, wheat; (g) grass fibers, such as from bamboo; (h)cellulose fibers from algae, such as velonia; (i) bacteria or fungi; and(j) parenchymal cells, such as from vegetables and fruits, and inparticular sugar beets, and citrus fruits such as lemons, limes,oranges, grapefruits. Microcrystalline forms of these cellulosematerials may also be used. Cellulose sources include (1) purified,optionally bleached, wood pulps produced from sulfite, kraft (sulfate),or prehydrolyzed kraft pulping processes and (2) purified cottonlinters. The source of the cellulose is not limiting, and any source maybe used including synthetic cellulose or cellulose analogs. According toone embodiment, the microfibrillar polysaccharide such as microfibrillarcellulose is derived from hardwood and/or softwood.

For purposes of the present invention polysaccharide microfibrils referto small diameter, high length-to-diameter ratio substructures which arecomparable in dimensions to those of cellulose microfibrils occurring innature. While the present specification refers to microfibrils andmicrofibrillation, these terms are here also meant to include (nano)fibrils with nanometer dimensions (cellulosic or other).

According to one embodiment, the microfibrillar polysaccharide, e.g.microfibrillar cellulose, is modified e.g. by means of grafting,cross-linking, chemical oxidation, for example by use of hydrogenperoxide, Fenton's reaction, and/or Tempo; physical modification such asadsorption, e.g. chemical adsorption; and enzymatic modification.Combined technologies may also be used to modify microfibrillarcellulose.

Cellulose can be found in nature in several hierarchical levels oforganization and orientation. Cellulose fibers comprise a layeredsecondary wall structure within which macrofibrils are arranged.Macrofibrils comprise multiple microfibrils which further comprisecellulose molecules arranged in crystalline and amorphous regions.Cellulose microfibrils range in diameter from about 5 to about 100nanometers for different species of plant, and are most typically in therange from about 25 to about 35 nanometers in diameter. The microfibrilsare present in bundles which run in parallel within a matrix ofamorphous hemicelluloses (specifically xyloglucans), pectinicpolysaccharides, lignins, and hydroxyproline rich glycoproteins(includes extensin). Microfibrils are spaced approximately 3-4 nm apartwith the space occupied by the matrix compounds listed above.

According to one embodiment, the polysaccharide is refined ordelaminated to such an extent that the final specific surface area(determined by adsorption of N₂ at 177 K according to the BET methodusing a Micromeritics ASAP 2010 instrument) of the formed microfibrillarpolysaccharide is from about 1 to about 100, such as from about 1.5 toabout 15, or from about 3 to about 10 m²/g. The viscosity of theobtained aqueous suspension of microfibrillar polysaccharide can be fromabout 200 to about 4000, or from about 500 to about 3000, or from about800 to about 2500 mPas. The stability, which is a measure of the degreeof sedimentation of the suspension, can be from about 60 to 100, such asfrom about 80 to about 100%, where 100% indicates no sedimentation for aperiod of at least 6 months.

According to one embodiment, the microfibrillar polysaccharide has anarithmetic fiber length from about 0.05 to about 0.5, for example fromabout 0.1 to about 0.4, or from about 0.15 to about 0.3 mm. According toone embodiment, the microfibrillar polysaccharide is added to thecellulosic suspension in an amount of from about 0.1 to about 50, forexample from about 0.5 to about 30, such as from about 1 to about 25 orfrom about 1 to about 15 or from about 1 to about 10 wt % based on theweight of the cellulosic product.

Non-delaminated wood fibers, e.g. cellulose fibers, are distinct frommicrofibrillar fibers because the fiber length of non-delaminated woodfibers ranges usually from about 0.7 to about 3 mm. The specific surfacearea of cellulosic fibers usually ranges from about 0.5 to about 1.5m²/g. Delamination can be carried out in various devices suitable fordelaminating the fibers of the polysaccharides. The prerequisite for theprocessing of the fibers is that the device is controlled in such waythat fibrils are released from the fiberwalls. This may be accomplishedby rubbing the fibers against each other, the walls or other parts ofthe device in which the delamination takes place. According to oneembodiment, the delamination is accomplished by means of pumping,mixing, heat, steam explosion, pressurization-depressurization cycle,impact grinding, ultrasound, microwave explosion, milling, andcombinations thereof. In any of the mechanical operations disclosedherein, it is important that sufficient energy is applied to providemicrofibrillar polysaccharide as defined herein.

According to one embodiment, the thermoplastic microspheres are expandedand added as pre-expanded microspheres or as unexpanded thermallyexpandable microspheres that preferably are expanded by heating duringthe cellulosic product production process, for example during a dryingstage where heat is applied, or in a separate process step, for examplein a cylinder heater or laminator. The microspheres may be expanded whenthe cellulosic product still is wet or when it is fully or almost fullydried. The microspheres are preferably added in the form of an aqueousslurry thereof, that optionally may contain other additives desirable tosupply to the stock. The amount of thermoplastic microspheres added canbe for example from about 0.01 to about 10, such as from about 0.05 toabout 10, for example from about 0.1 to about 10, from about 0.1 toabout 5, or from about 0.4 to about 4 wt % based on the weight ofcellulosic product.

According to one embodiment, thermally expandable thermoplasticmicrospheres as referred to herein comprise a thermoplastic polymershell encapsulating a propellant. The propellant is preferably a liquidhaving a boiling temperature not higher than the softening temperatureof the thermoplastic polymer shell. Upon heating, the propellantincreases the internal pressure at the same time as the shell softensresulting in significant expansion of the microspheres. Both expandableand pre-expanded thermoplastic microspheres are commercially availableunder the trademark Expancel© (Akzo Nobel) and are marketed in variousforms, e.g. as dry free flowing particles, as an aqueous slurry or as apartially dewatered wet-cake. They are also well described in theliterature, for example in U.S. Pat. Nos. 3,615,972, 3,945,956,4,287,308, 5,536,756, 6,235,800, 6,235,394 and 6,509,384, in US PatentApplications Publication 2005/0079352, in EP 486080 and EP 1288272, inWO 2004/072160, WO 2007/091960 and WO 2007/091961 and in JP Laid OpenNo. 1987-286534, 2005-213379 and 2005-272633.

According to one embodiment, the thermoplastic polymer shell of thethermoplastic microspheres is preferably made of a homo- or co-polymerobtained by polymerising unsaturated monomers. Those monomers can, forexample, be nitrile containing monomers such as acrylonitrile,methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile,fumaronitrile or crotonitrile; acrylic esters such as methyl acrylate orethyl acrylate; methacrylic esters such as methyl methacrylate,isobornyl methacrylate or ethyl methacrylate; vinyl halides such asvinyl chloride; vinyl esters such as vinyl acetate, vinyl ethers such asalkyl vinyl ethers like methyl vinyl ether or ethyl vinyl ether, othervinyl monomers such as vinyl pyridine; vinylidene halides such asvinylidene chloride; styrenes such as styrene, halogenated styrenes orα-methyl styrene; or dienes such as butadiene, isoprene and chloroprene.Any mixtures of the above mentioned monomers may also be used.

According to one embodiment, the propellant of the thermoplasticmicrospheres comprises hydrocarbons such as propane, butane, isobutane,n-pentane, isopentane, neopentane, hexane, isohexane, neohexane,heptane, isoheptane, octane or isooctane, or mixtures thereof. Asidefrom them, other hydrocarbon types can also be used, such as petroleumether, or chlorinated or fluorinated hydrocarbons, such as methylchloride, methylene chloride, dichloroethane, dichloroethylene,trichloroethane, trichloroethylene, trichlorofluoromethane,perfluorinated hydrocarbons, etc.

According to one embodiment, the expandable thermoplastic microspheressuitable for the invention have a volume median diameter from about 1 toabout 500 μm, for example from about 5 to about 100 μm, or from about 10to about 50 μm. The temperature at which the expansion starts, referredto as T_(start), is preferably from about 60 to about 150° C., mostpreferably from about 70 to about 100° C. The temperature at whichmaximum expansion is reached, referred to as T_(max), is preferably fromabout 90 to about 180° C., most preferably from about 115 to about 150°C.

According to one embodiment, pre-expanded thermoplastic microspheressuitable for the invention have a volume median diameter from about 10to about 120 μm, most preferably from about 20 to about 80 μm. Thedensity is preferably from about 5 to about 150 g/dm³, most preferablyfrom about 10 to about 100 g/dm³. Even though pre-expanded thermoplasticmicrospheres are commercially available as such, it is also possible toprovide them by thermal on-site expansion of unexpanded expandablethermoplastic microspheres, for example just before they are added tothe stock, which is facilitated if the expandable microspheres have aT_(start) below about 100° C. so steam can be used as a heating medium.

According to one embodiment, the weight ratio of microfibrillarpolysaccharide to thermoplastic microspheres added to the aqueoussuspension ranges from about 1:100 to about 200:1, for example fromabout 1:20 to about 40:1 or from about 1:5 to about 20:1 or from about1:2 to about 10:1 or from about 1:1 to about 8:1 or from about 2:1 toabout 5:1. According to one embodiment, the microfibrillarpolysaccharide and the thermoplastic microspheres are added separatelyin any order. According to one embodiment, microfibrillar polysaccharideand thermoplastic microspheres are added as a premix. According to oneembodiment, the premix further comprises at least one polyelectrolyte,such as a cationic polyelectrolyte.

According to one embodiment, the cellulosic product is a laminate. Bythe term “laminate” is meant a cellulosic product comprising at leasttwo layers of paper and/or board. However, the laminate may also containfurther layers of other material than paper and/or board including filmsof various polymers, e.g. polyethylene, polypropylene, polyester,polyvinyl and/or polyvinylidene chloride, polyvinyl alcohol (PVOH),polyethylene vinyl alcohol co-polymer, ethylene vinyl acetateco-polymers and cellulose esters in one or more layers and/or a metalliclayer, e.g. an aluminum film, SiO_(x)-(where 0<x<=2)) deposited polymerfilms, silica-blended polyvinyl alcohol (PVOH) as further disclosed inUS2006/135676 or metallized polymer film which may function as barrierfor gases and which may have low or no permeability to water, steam,carbon dioxide, and oxygen. Examples of suitable oxygen barriers includeethylene vinyl alcohol (EVOH), polyvinylidene chloride (PVDC), PAN(polyacrylo nitrile), aluminum, metallized films, e.g. of polypropyleneor polyethylene terephthalate, SiO_(x)-deposited films (where 0<x<=2),inorganic plate-shaped mineral compounded polymers such as claycompounded polymers.

According to one embodiment, the laminate is a packaging laminatecomprising at least one cellulosic layer, at least one liquid barrierlayer and at least one gas barrier layer, said paper or paperboardcomprising, preferably at least at the edges thereof, expanded orunexpanded expandable thermoplastic microspheres.

According to one embodiment, the cellulosic product is a liquidpackaging laminate comprising three layers paper or paperboard, of whichpreferably at least the middle layer comprises microfibrillarpolysaccharide and/or thermoplastic microspheres.

According to one embodiment, the packaging laminate comprises at leastone, preferably at least two liquid barrier layers on each side of thepaper or paperboard base layer(s). A liquid barrier layer may be made ofany material that show no or insignificant permeability to water.Suitable materials include polymers of polyethylene like high density orlinear low density polyethylene, polypropylene, PVC, polyesters likepolyethylene terephthalate, and physical or mechanical mixtures thereof.Also co-polymers can be used, such as co-polymers of ethylene andpropylene. The liquid barrier layer(s) can be applied in any known ways,such as various lamination methods or the like.

According to one embodiment, the packaging laminate may further comprisea gas barrier layer, preferably between a base layer and a liquidnon-permeable layer intended to face the inside of the package. Anymaterial that show no or insignificant permeability to molecular oxygencan be used. Examples of materials include metal foils like aluminiumfoils, silica coating, e.g. applied in a coating composition comprisingcolloidal silica and optionally various additives as described in WO2006/065196, or produced by plasma deposition. Other possible materialsinclude polymers like polyvinyl alcohol or co-polymers of ethylene andvinyl alcohol. A gas barrier layer can be applied in any known way, suchas various laminating methods or the like.

According to one embodiment, the invention concerns a process for theproduction of a packaging laminate comprising a step of applying leastone liquid barrier layer and at least one gas barrier layer to a sheetor web of paper or paperboard comprising, preferably at least at theedges thereof, expanded or unexpanded expandable thermoplasticmicrospheres.

According to one embodiment, the cellulosic product is a sealed packagefor food or beverage products made of a packaging laminate comprising atleast one base layer of paper or paperboard and at least one liquidbarrier layer, and preferably at least one gas barrier layer, said paperor paperboard comprising, preferably at least at the edges thereof,expanded or unexpanded expandable thermoplastic microspheres.

According to one embodiment, in a single layer cellulosic product, thegrammage is from about 40 to about 1500 g/m², such as from about 60 toabout 700 or from about 80 to about 600, such as from about 90 to about500 or from about 100 to about 500 g/m². The density is preferably fromabout 100 to about 1200 such as from about 150 to about 1000 or fromabout 200 to about 800 kg/m³.

According to one embodiment, in a cellulosic product of two layer boardthe grammage, per layer, is from about 25 to about 750 g/m², such asfrom about 50 to about 400 or from about 100 to about 300 g/m². Thedensity of two layers is preferably from about 300 to about 1200 kg/m³,most preferably from about 400 to about 1000 kg/m³ or from about 450 toabout 900 kg/m³. The total gram mage is preferably from about 50 toabout 1500 g/m², most preferably from about 100 to about 800 or fromabout 200 to about 600 g/m². The total density is preferably from about300 to about 1200 kg/m³, most preferably from about 400 to about 1000kg/m³ or from about 450 to about 900 kg/m³.

According to one embodiment, in a cellulosic product of three or morelayers the outer layers have a grammage from about 10 to about 750, suchas from about 20 to about 400 or from about 30 to about 200 g/m². Thedensity of the outer layers is preferably from about 300 to about 1200kg/m³, most preferably from about 400 to about 1000 kg/m³ or from about450 to about 900 kg/m³. The centre, or non-outer, layer or layerspreferably have a grammage from about 10 to about 750 g/m², mostpreferably from about 25 to about 400 g/m² or from about 50 to about 200g/m². The density of the centre, or non-outer layer or layers arepreferably from about 10 to about 800 kg/m³, most preferably from about50 to about 700 kg/m³ or from about 100 to about 600 kg/m³. The totalgrammage is preferably from about 30 to about 2250 g/m², most preferablyfrom about 65 to about 800 g/m² or from about 110 to about 600 g/m². Thetotal density is preferably from about 100 to about 1000 kg/m³, mostpreferably from about 200 to about 900 kg/m³ or from about 400 to about800 kg/m³.

According to one embodiment, the cellulosic product has separate layersfor providing liquid and gas barriers, respectively, but in anembodiment a liquid barrier layer and a gas barrier layer is provided bya single layer of a material having both liquid and gas barrierproperties.

According to one embodiment, a multilayered cellulosic product can beproduced by forming the individual layers separately in one or severalweb-forming units and then couching them together in the wet state.Examples of suitable grades of multilayered cellulosic product of theinvention include those comprising from three to seven layers comprisingcellulosic fibers and at least one of said cellulosic layers comprisingthermoplastic microspheres and microfibrillar polysaccharide. Inmultilayered cellulosic products with three or more layers, such as atleast one of the middle layers comprises thermoplastic microspheres andmicrofibrillar polysaccharide.

According to one embodiment, at least one layer of the cellulosicproduct can be formed and pressed in a separate stage before beinglaminated to a further layer. Following the pressing stage, the laminatecan be dried in conventional drying equipment such as cylinder dryerwith or without dryer wire/felt, air dryer, metal belt etc. Followingdrying or during the drying process, the laminate can be coated with afurther layer.

According to one embodiment, the aqueous suspension contains cellulosicfibers from chemical pulp, such as sulfate (kraft) and sulfite pulp,organosolv pulp; recycled fibers; and/or mechanical pulp including e.g.refiner mechanical pulp (RMP), pressurized refiner mechanical pulp(PRMP), pretreatment refiner chemical alkaline peroxide mechanical pulp(P-RC APMP), thermomechanical pulp (TMP), thermomechanical chemical pulp(TMCP), high-temperature TMP (HT-TMP) RTS-TMP, alkaline peroxide pulp(APP), alkaline peroxide mechanical pulp (APMP), alkaline peroxidethermomechanical pulp (APTMP), thermopulp, groundwood pulp (GW), stonegroundwood pulp (SGW), pressure groundwood pulp (PGW), super pressuregroundwood pulp (PGW-S), thermo groundwood pulp (TGW), thermo stonegroundwood pulp (TSGW), chemimechanical pulp (CMP),chemirefinermechanical pulp (CRMP), chemithermomechanical pulp (CTMP),high-temperature CTMP(HT-CTMP), sulfite-modified thermomechanical pulp(SMTMP), reject CTMP (CTMP_(R)), groundwood CTMP (G-CTMP), semichemicalpulp (SC), neutral sulfite semi chemical pulp (NSSC), high-yield sulfitepulp (HYS), biomechanical pulp (BRMP), pulps produced according to theOPCO process, explosion pulping process, Bi-V is process, dilution watersulfonation process (DWS), sulfonated long fibers process (SLF),chemically treated long fibers process (CTLF), long fiber CMP process(LFCMP), and modifications and combinations thereof. The pulp may be ableached or non-bleached pulp. According to one embodiment, the aqueoussuspension contains mechanical, recycled and/or kraft pulp.

Cellulosic fibers can be derived from hardwood, softwood species, and/ornonwood. Examples of hardwood and softwood include birch, beech, aspensuch as European aspen, alder, Eucalyptus, maple, acacia, mixed tropicalhardwood, pine such as loblolly pine, fir, hemlock, larch, spruce suchas Black spruce or Norway spruce, and mixtures thereof. Non-wood plantraw material can be provided from e.g. straws of grain crops, wheatstraw reed canary grass, reeds, flax, hemp, kenaf, jute, ramie, seed,sisal, abaca, coir, bamboo, bagasse or combinations thereof.

According to one embodiment, the cellulosic fibers of the aqueoussuspension are derived from hardwood and/or softwood species.

According to one embodiment, at least one outer layer of the cellulosicproduct is produced from a chemical pulp obtained in accordance with anyof the methods as disclosed herein or other conventional methods forobtaining chemical pulp. The pulps may be bleached or unbleached.

According to one embodiment, a laminate, for example a board such as aliquid packaging board, comprising at least three layers is formedwhereby the product is obtained by joining directly or indirectly aninner layer formed from an aqueous suspension comprising microfibrillarpolysaccharide and optionally thermoplastic microspheres and furtherlayers joined to said inner layer's respective sides, said furtherlayers being produced from an aqueous suspension with or withoutmicrofibrillar polysaccharide and optionally thermoplastic microspheres.

Further layers, e.g. barrier layers, may be formed and joined on theouter layers as defined. Any of the layers can also be coated to improvee.g. printability of the laminate. According to one embodiment, anycoated or non-coated layer may in turn be coated with a plastic orpolymer layer. Such coating may further reduce liquid penetration andimprove heat-sealing properties of the product.

According to one embodiment, at least one layer of a laminate isproduced from a mechanical and/or chemical pulp obtained from wood ornonwood pulp in accordance with any of the methods as disclosed hereinor other conventional methods for obtaining pulp. According to oneembodiment, the layer is produced from at least about 40, e.g. at leastabout 50, for example at least about 60 or at least about 75 wt %mechanical pulp based on the total pulp weight. The pulps may bebleached or unbleached.

According to one embodiment, the aqueous suspension has a consistency ofcellulosic fibers in an amount from about 0.01 to about 50, for examplefrom about 0.1 to about 25 or from about 0.1 to about 10 wt %.

According to one embodiment, the aqueous suspension contains mineralfillers of conventional types, such as, for example, kaolin, clay,titanium dioxide, gypsum, talc and both natural and synthetic calciumcarbonates, such as, for example, chalk, ground marble, ground calciumcarbonate, and precipitated calcium carbonate. The aqueous suspensioncan also contain papermaking additives of conventional types, such asdrainage and retention chemicals, dry strength agents, sizing agents,such as those based on rosin, ketene dimers, ketene multimers, alkenylsuccinic anhydrides, etc.

The cellulosic product may further comprise a wet strength agent that isadded to the stock before dewatering. Suitable wet strength agentsinclude resins of polyamine epihalohydrin, polyamide epihalohydrin,polyaminoamide epihalohydrin, urea/formaldehyde,urea/melamine/formaldehyde, phenol/formaldehyde, polyacrylicamide/glyoxal condensate, polyvinyl amine, poly-urethane,polyisocyanate, and mixtures thereof, of which polyaminoamideepichlorohydrin (PAAE) is particularly preferred.

According to one embodiment, wet and dry strength agents may be added inamounts from about 0.1 to about 30 kg/t cellulosic product, such as fromabout 0.5 to about 10 kg/t pulp. According to one embodiment, sizingagent(s) may be added in amounts from about 0.1 to about 10, such asfrom about 0.5 to about 4 kg/t cellulosic product. Further paperchemicals may be added to the aqueous suspension in conventional mannerand amounts.

According to one embodiment, the invention is applied on paper machinesproducing wood-containing paper or board and/or paper or board based onrecycled fibers, different types of book and newsprint papers, and/or onmachines producing nonwood-containing printing and writing papers.

According to one embodiment, the invention further concerns acomposition comprising microfibrillar polysaccharide and thermoplasticmicrospheres as disclosed herein. According to one embodiment, thecomposition is aqueous. According to one embodiment, the weight ratio ofmicrofibrillar polysaccharide to thermoplastic microspheres in thecomposition ranges from about 1:100 to about 200:1, for example fromabout 1:20 to about 40:1 or from about 1:5 to about 20:1 or from about1:2 to about 10:1 or from about 1:1 to about 8:1 or from about 2:1 toabout 5:1.

According to one embodiment, the invention further concerns the use ofthe composition in the production of a cellulosic product.

The invention also regards a cellulosic product obtainable by theprocess as defined herein. The invention also regards a cellulosicproduct comprising microfibrillar polysaccharide and thermoplasticmicrospheres. The invention also regards a single layer cellulosicproduct comprising microfibrillar polysaccharide. The invention alsoregards a single layer cellulosic product comprising microfibrillarpolysaccharide and optionally thermoplastic microspheres.

According to one embodiment, the weight ratio of microfibrillarpolysaccharide to thermoplastic microspheres in the cellulosic productranges from about 1:100 to about 200:1, for example from about 1:20 toabout 40:1 or from about 1:5 to about 20:1 or from about 1:2 to about10:1 or from about 1:1 to about 8:1 or from about 2:1 to about 5:1.According to one embodiment, the composition comprises an electrolytesuch as a cationic electrolyte.

According to one embodiment, the cellulosic product may be any of thoseobtained herein including any of their properties. For example, thegrammage can be within the ranges as defined herein. According to oneembodiment, the cellulosic product may comprise any pulp as disclosedherein, especially mechanical pulp, recycled pulp and/or kraft pulp.

The invention also concerns the use of the cellulosic product, e.g. asliquid packaging board, folding box board, or liner. According to oneembodiment, the product is used in the form of a packaging laminate,which may be used for the production of sealed packages for liquid, foodor non-food products. According to one embodiment, the inventionconcerns the use of a cellulosic product for the production of a sealedpackage comprising the steps of forming a container from a packaginglaminate, filling the container with a food or beverage product, andsealing the container, wherein said packaging laminate comprises atleast one base layer of paper or paperboard and at least one liquidbarrier layer, and preferably at least one gas barrier layer, said paperor paperboard comprising, preferably at least at the edges thereof,expanded or unexpanded expandable thermoplastic microspheres.

In one embodiment the cellulosic product is used for packaging of foodthat do not need to be heat treated after the package has been filledand sealed. Usually such packages are used for beverages like milk,juice and other soft drinks, soups, and tomato products.

In another embodiment the cellulosic product package is used for food orbeverages where the filled and sealed package is heat treated toincrease the shelf life of the content. Such packages can be used forall kinds of food products, particularly those traditionally beingpacked in tin cans, and will herein be referred to as retortablepackages and the material therefore as retortable packaging laminate orretortable board. Desired properties of a retortable packaging laminateinclude ability to withstand treatment with saturated steam at a hightemperature and pressure, for example from about 110 to about 150° C. ata time from about 30 minutes to about 3 hours.

The invention being thus described, it will be obvious that the same maybe varied in many ways. The following examples will further illustratehow the described invention may be performed without limiting the scopeof it.

All parts and percentages refer to part and percent by weight, if nototherwise stated.

EXAMPLE 1

A) A single layer cellulosic product (A1) with a grammage ofapproximately 170 g/m² was produced from Timsfors test liner (ShopperRiegler 47) using a dynamic sheet former (Formette Dynamic, supplied byFibertech AB, Sweden). Paper sheets were formed in the Dynamic SheetFormer by pumping the stock (pulp consistency: 0.5%, conductivity 2000μm/s, pH 7) from the mixing chest through a transversing nozzle into therotating drum onto the water film on top of the wire, draining the stockto form a sheet, pressing and drying the sheet. The amounts of chemicalsadded to the suspension (based on the weight of cellulosic product) andaddition time (in seconds) prior to pumping and sheet formation were thefollowing:

TABLE 1 Time (s) Amount (%) Product Chemical 120 0 PC155 or Anionicpotato starch or BMC MFC (microfibrillar cellulose) 60 0.2 Eka DR 28HFAKD (alkyl ketene dimer) 45 0.6 Perlbond 970 Cationic potato starch 300.03 Eka PL1510 Cationic polyacrylamide 15 0.05 NP442 Colloidal silicasol 0 PumpingThe dewatering time was 90 s. The paper sheets were pressed at 3 bars ina roll press and thereafter dried restrained in a plane drier at 105° C.for 16 minutes.

B) Single layer cellulosic products with a grammage of approximately 170g/m² were prepared as in A), but with addition of 2 and 5% (based on theweight of cellulosic product) PC155 (anionic potato starch) respectively(B1-B2).

C) Single layer paper products with a grammage of approximately 170 g/m²were prepared as in A), but with addition of 2, 5 and 10% (based on theweight of cellulosic product) microfibrillar cellulose (prepared fromunbleached kraft pulp from Södra Cell AB, Sweden) (C₁-C₃). Thecharacteristics of the microfibrillar cellulose were as follows: Fiberlength: 0.29 mm (Kajaani FS-100 Fiber Size Analyser), specific surfacearea 5 g/m² (BET method using a Micrometrics ASAP 2010 instrument),viscosity: 808 mpas, stability:100% (sedimentation degree of a 0.5% pulpsuspension: Water Retention Value (WRV): 4.0 (g/g) (SCAN-C 62:00).

Single layer cellulosic products prepared according to A), B) and C)were analyzed for their grammage, density, tensile strength, burststrength, Z-strength, geometrical bending resistance and porosity (seeTable 2).

TABLE 2 A B C Paper Property Unit 1 1 2 1 2 3 Density kg/m³ 572 569 580576 590 613 Tensile Index Nm/g 50.8 51.8 54.8 55.3 60.4 65.6 TensileStiffness kNm/g 6.0 6.0 6.1 6.3 6.6 7.0 Index Bending Nm⁶/kg³ 12.3 12.212.4 12.8 13.0 13.1 Resistance Index Geom. Bending mN 58 58 61 59 60 61Resistance Z-Strength kPa 565 547 564 591 599 649 Burst Index kPa m²/g3.3 3.2 3.5 3.6 3.8 4.3 Bendtsen Porosity ml/min 308 325 305 272 182 80

EXAMPLE 2

A) A single layer cellulosic product (A1) with a grammage ofapproximately 170 g/m² was produced from a CTMP-pulp (CSF 400) fromSödra Cell AB using a dynamic sheet former (Formette Dynamic, suppliedby Fibertech AB, Sweden). Paper sheets were formed as in Example 1, butwith a pulp conductivity of 1500 μm/s. The amounts of chemicals added tothe suspension (based on the weight of cellulosic product) and additiontime (in seconds) prior to pumping and sheet formation were as inExample 1. The sheets were drained, pressed and dried as in Example 1.

B) Single layer cellulosic products with a grammage of approximately 170g/m² were prepared as in A), but with addition of 2 and 5% (based on theweight of cellulosic product) PC155 (anionic potato starch),respectively (B1-B2).

C) Single layer cellulosic products with a grammage of approximately 170g/m² were prepared as in A), but with addition of 2, 5 and 10% (based onthe weight of cellulosic product) microfibrillar cellulose (preparedfrom fully bleached birch kraft pulp fibers from Iggesund) (C₁-C₃). Thecharacteristics of the microfibrillar cellulose were the following:Fiber length: 0.37 mm (L&W Fiber Tester), stability: 94% (sedimentationdegree of a 0.5% pulp suspension: Water Retention Value (WRV): 6.8 (g/g)(SCAN-C 62:00).

Single layer cellulosic products prepared according to A), B) and C)were analyzed for their grammage, density, tensile strength, burststrength, Z-strength, geometrical bending resistance and porosity (seeTable 3).

TABLE 3 Paper A B C Property Unit 1 1 2 1 2 3 Density kg/m³ 331 320 335342 363 401 Tensile Nm/g 30.7 31.0 32.7 35.5 41.2 49.4 Index TensilekNm/g 3.7 3.6 3.8 4.0 4.5 4.8 Stiffness Index Bending Nm⁶/ 26.1 27.523.0 27.2 24.9 24.4 Resistance kg³ Index Geom. mN 165 171 134 170 151146 Bending Resistance Z-Strength kPa 214 220 246 275 296 416 BurstIndex kPa 1.9 1.6 2.0 1.8 2.4 2.6 m²/g Bendtsen ml/min 1775 1500 1150912 675 228 Porosity

EXAMPLE 3

-   -   A) A single layer cellulosic product (A1) with a grammage of        approximately 170 g/m² were produced from Timsfors test liner        using a dynamic sheet former (Formette Dynamic, supplied by        Fibertech AB, Sweden) as in Example 1, but without chemicals.        Paper sheets were formed, drained, pressed and dried as in        Example 1.    -   B) Single layer cellulosic products with a grammage of 170 g/m²        were prepared as in A), but with addition of 2, 5 and 10% (based        on the weight of cellulosic product) microfibrillar cellulose        (prepared from unbleached kraft pulp from Södra Cell AB, Sweden)        (B1-B3). The characteristics of the microfibrillar cellulose        were the following: Fiber length: 0.29 mm (Kajaani FS-100 Fiber        Size Analyser), specific surface area 5 g/m² (BET method using a        Micrometrics ASAP 2010 instrument), viscosity: 808 mPas,        stability:100% (sedimentation degree of a 0.5% pulp suspension:        Water Retention Value (WRV): 4.0 (g/g) (SCAN-C 62:00).

Paper products prepared according to A) and B) were analyzed for theirgrammage, density, tensile strength, burst strength, Z-strength,geometrical bending resistance and porosity (see Table 4).

TABLE 4 A B Paper Property Unit 1 1 2 3 Density kg/m³ 569 574 590 609Tensile Index Nm/g 46.3 56.2 56.2 60.7 Tensile Stiffness Index kNm/g 5.86.3 6.4 6.9 Bending Resistance Index Nm⁶/kg³ 12.0 11.8 12.1 13.0 Geom.Bending Resistance mN 48 56 54 47 Z-Strength kPa 443 581 566 612 BurstIndex kPa m²/g 2.9 3.4 3.6 4.1 Bendtsen Porosity ml/min 232 275 122 62

EXAMPLE 4

-   -   A) A single layer cellulosic product (A1) with a grammage of        approximately 170 g/m² was produced from a CTMP-pulp (CSF 400)        from Södra Cell AB using a dynamic sheet former (Formette        Dynamic, supplied by Fibertech AB, Sweden) as in Example 1, but        without chemicals. Paper sheets were formed, drained, pressed        and dried as in Example 1.    -   B) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in A), but with addition        of 2, 5 and 10% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from fully bleached birch        kraft pulp fibers from Iggesund) (B1-B3). The characteristics of        the microfibrillar cellulose were the following: Fiber length:        0.37 mm (L&W Fiber Tester), stability: 94% (sedimentation degree        of a 0.5% pulp suspension: Water Retention Value (WRV): 6.8        (g/g) (SCAN-C 62:00).

Single layer cellulosic products prepared according to A) and B) wereanalyzed for their grammage, density, tensile strength, burst strength,Z-strength, geometrical bending resistance and porosity (see Table 5).

TABLE 5 A B Paper Property Unit 1 1 2 3 Density kg/m³ 310 348 378 391Tensile Index Nm/g 30.3 32.0 36.1 43.1 Tensile Stiffness Index kNm/g 3.33.9 4.3 4.6 Bending Resistance Index Nm⁶/kg³ 22.3 21.8 21.8 22.2 Geom.Bending Resistance mN 99 131 134 118 Z-Strength kPa 93 218 267 336 BurstIndex kPa m²/g 0.8 1.7 2.1 2.4 Bendtsen Porosity ml/min 505 729 270 205

EXAMPLE 5

-   -   A) A single layer cellulosic product (A1) with a grammage of        approximately 170 g/m² was produced from Timsfors test liner        (Shopper Riegler 47) using a dynamic sheet former (Formette        Dynamic, supplied by Fibertech AB, Sweden). Paper sheets were        formed in the Dynamic Sheet Former by pumping the stock (pulp        consistency: 0.5%, conductivity 2000 μm/s, pH 7) from the mixing        chest through a transversing nozzle into the rotating drum onto        the water film on top of the wire, draining the stock to form a        sheet, pressing and drying the sheet. The amounts of chemicals        added to the suspension (based on the weight of cellulosic        product) and addition time (in seconds) prior to pumping and        sheet formation were the following

TABLE 6 Time (s) Amount (%) Product Chemical 145 0 BMC MFC(microfibrillar cellulose) 120 0.13 Eka WS XO PAAE (polyamidoamineepichlorohydrine) 75 0.2 Eka DR 28HF AKD (alkyl ketene dimer) 60 0.6Perlbond 970 Cationic potato starch 45 0 820 SL 80 Thermoplasticmicrosphere or Premix of MFC and 820 SL 80 30 0.03 Eka PL1510 Cationicpolyacrylamide 15 0.05 NP442 Colloidal silica sol 0 PumpingThe dewatering time was 90 s. The paper sheets were pressed at 4.85 barsin a plane press for 7 minutes and thereafter dried in a photo drier(Japo automatic glazing drier) at 120° C.

-   -   B) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in A), but with addition        of 1 and 2% (based on the weight of cellulosic product) 820 SL        80 (B1-B2).    -   C) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in A), but 1% of 820 SL        80 was premixed with 5, 10 and 15% (based on the weight of        cellulosic product) microfibrillar cellulose (prepared from        unbleached kraft pulp from Södra Cell AB, Sweden) (C₁-C₃). The        characteristics of the microfibrillar cellulose were the        following: Fiber length: 0.29 mm (Kajaani FS-100 Fiber Size        Analyser), specific surface area 5 g/m² (BET method using a        Micrometrics ASAP 2010 instrument), viscosity: 808 mPas,        stability:100% (sedimentation degree of a 0.5% pulp suspension:        Water Retention Value (WRV): 4.0 (g/g) (SCAN-C 62:00).    -   D) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in A), but 2% of 820 SL        80 was premixed with 5, 10 and 15% (based on the weight of        cellulosic product) microfibrillar cellulose (prepared from        unbleached kraft pulp from Södra Cell AB, Sweden) (D1-D3). The        characteristics of the microfibrillar cellulose were as in C).    -   E) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in B), but with addition        of 10% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from unbleached kraft pulp        from Södra Cell AB, Sweden) (E1-E2). The characteristics of the        microfibrillar cellulose were as in C).

Single layer cellulosic products prepared according to A), B), C), D)and E) were analyzed for their grammage, density, tensile strength,burst strength, Z-strength, geometrical bending resistance, edge wickand porosity (see Table 7a and 7b).

TABLE 7a A B C Paper Property Unit 1 1 2 1 2 3 Density kg/m³ 669 539 441581 612 637 Tensile Index Nm/g 48.0 40.3 36.7 46.1 50.5 52.1 TensileStiffness kNm/g 4.9 3.9 3.4 4.2 4.7 4.7 Index Bending Nm⁶/kg³ 8.3 13.317.9 11.6 9.9 8.9 Resistance Index Geom. Bending mN 47 73 95 66 59 53Resistance Z-Strength kPa 642 561 395 656 719 721 Burst Index kPa m²/g4.0 3.2 2.8 3.8 4.2 4.9 Edge wick kg/m² 1.7 1.6 1.7 1.4 1.2 1.2 BendtsenPorosity ml/min 129 392 650 178 88 50

TABLE 7b D E Paper Property Unit 1 2 3 1 2 Density kg/m³ 492 502 499 638511 Tensile Index Nm/g 41.1 46.2 47.5 51.1 47.0 Tensile Stiffness IndexkNm/g 3.6 4.0 4.2 4.7 3.9 Bending Resistance Nm⁶/kg³ 14.9 13.4 12.1 9.113.6 Index Geom. Bending mN 87 79 67 59 83 Resistance Z-Strength kPa 526618 670 712 587 Burst Index kPa m²/g 3.5 3.9 4.4 4.4 4.0 Edge wick kg/m²1.5 1.5 1.1 1.3 1.5 Bendtsen Porosity ml/min 302 162 70 60 132

EXAMPLE 6

-   -   A) A single layer cellulosic product (A1) with a grammage of        approximately 170 g/m² was produced from a hardwood CTMP-pulp        (CSF 465) from M-real using a dynamic sheet former (Formette        Dynamic, supplied by Fibertech AB, Sweden). Paper sheets were        formed in the Dynamic Sheet Former by pumping the stock (pulp        consistency: 0.5%, conductivity 1500 μm/s, pH 7) from the mixing        chest through a transversing nozzle into the rotating drum onto        the water film on top of the wire, draining the stock to form a        sheet, pressing and drying the sheet. The amounts of chemicals        added to the suspension (based on the weight of cellulosic        product) and addition time (in seconds) prior to pumping and        sheet formation were as follows:

TABLE 8 Time (s) Amount (%) Product Chemical 145 0 BMC MFC(microfibrillar cellulose) 120 0.13 Eka WS XO PAAE (polyamidoamineepichlorohydrine) 75 0.2 Eka DR 28HF AKD (alkyl ketene dimer) 60 0.6Perlbond 970 Cationic potato starch 45 0 820 SL 80 Thermoplasticmicrospheres or Premix of MFC and 820 SL 80 30 0.03 Eka PL1510 Cationicpolyacrylamide 15 0.05 NP442 Colloidal silica sol 0 PumpingThe dewatering time was 90 s. The paper sheets were pressed at 4.85 barsin a plane press for 7 minutes and thereafter dried in a photo drier(Japo automatic glazing drier) at 120° C.

-   -   B) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in A), but with addition        of 1 and 2% (based on the weight of cellulosic product) 820 SL        80, (B1-B2).    -   C) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in A), but 1% of 820 SL        80 was premixed with 5, 10 and 15% (based on the weight of        cellulosic product) microfibrillar cellulose (prepared from a        ECF-bleached Eucalyptus Globulus kraft pulp from Portugal)        (C₁-C₃). The characteristics of the microfibrillar cellulose        were the following: Fiber length: 0.41 mm ((L&W Fiber Tester)        and stability:94% (sedimentation degree of a 0.5% pulp        suspension; water retention value (WRV): 6.8 g/g.    -   D) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in A), but 2% of 820 SL        80 was premixed with 5, 10 and 15% (based on the weight of        cellulosic product) microfibrillar cellulose (prepared from        unbleached kraft pulp from Södra Cell AB, Sweden) (D1-D3). The        characteristics of the microfibrillar cellulose were as in C).    -   E) Single layer cellulosic products with a grammage of        approximately 170 g/m² were prepared as in B), but with addition        of 10% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from unbleached kraft pulp        from Södra Cell AB, Sweden) (E1-E2). The characteristics of the        microfibrillar cellulose were as in C):

Single layer cellulosic products prepared according to A), B), C), D)and E) were analyzed for their grammage, density, tensile strength,burst strength, Z-strength, geometrical bending resistance, edge wickand porosity (see Table 9a and 9b).

TABLE 9a A B C Paper Property Unit 1 1 2 1 2 3 Density kg/m³ 399 326 283363 401 403 Tensile Index Nm/g 20.0 17.2 13.8 22.2 28.0 35.0 TensileStiffness Index kNm/g 3.0 2.5 1.8 2.9 3.3 3.9 Bending Resistance IndexNm⁶/kg³ 16.0 20.7 22.1 19.2 15.6 15.5 Geom. Bending Resistance mN 68 9296 88 82 73 Z-Strength kPa 262 175 149 293 363 509 Burst Index kPa m²/g0.69 0.52 0.48 0.89 1.50 1.96 Edge wick kg/m² 7.6 7.3 7.3 6.3 5.4 4.3Bendtsen Porosity ml/min 2138 2412 2750 1700 975 462

TABLE 9b D E Paper Property Unit 1 2 3 1 2 Density kg/m³ 320 345 365 393359 Tensile Index Nm/g 18.9 23.6 31.2 29.1 25.8 Tensile kNm/g 2.4 2.83.4 3.4 3.0 Stiffness Index Bending Nm⁶/ 21.5 21.3 18.4 18.8 21.6Resistance kg³ Index Geom. Bending mN 96 96 93 90 103 ResistanceZ-Strength kPa 279 299 423 279 313 Burst Index kPa 0.78 1.15 1.47 1.461.29 m²/g Edge wick kg/m² 6.4 5.8 4.8 4.9 4.8 Bendtsen ml/min 2225 1575550 975 1050 Porosity

EXAMPLE 7

-   -   A) Single layer cellulosic products (A1-A5) with a grammage of        approximately 100, 150, 190, 230 and 280 g/m² were produced from        a softwood CTMP pulp from Östrand (CSF 500) using a dynamic        sheet former (Formette Dynamic, supplied by Fibertech AB,        Sweden). Paper sheets were formed in the Dynamic Sheet Former by        pumping the stock (pulp consistency: 0.5%, conductivity 1500        μm/s, pH 7) from the mixing chest through a transversing nozzle        into the rotating drum onto the water film on top of the wire,        draining the stock to form a sheet, pressing and drying the        sheet. The amounts of chemicals added to the suspension (based        on the weight of cellulosic product) and addition time (in        seconds) prior to pumping and sheet formation were the        following:

TABLE 10 Time (s) Amount (%) Product Chemical 145 0 BMC MFC(microfibrillar cellulose) 120 0.13 Eka WS XO PAAE (polyamidoamineepichlorohydrine) 75 0.2 Eka DR 28HF AKD (alkyl ketene dimer) 60 0.6Perlbond 970 Cationic potato starch 45 0 820 SL 80 Thermoplasticmicrospheres 30 0.03 Eka PL1510 Cationic polyacrylamide 15 0.05 NP442Colloidal silica sol 0 PumpingThe dewatering time was 90 s. The paper sheets were pressed at 4.85 barsin a plane press for 7 minutes and thereafter dried in a photo drier(Japo automatic glazing drier) at 120° C.

-   -   B) Single layer cellulosic products with a grammage of        approximately 100, 150 and 190 g/m² were prepared as in A), but        with addition of 2% (based on the weight of cellulosic product)        820 SL 80, (B1-B3).    -   C) Single layer cellulosic products with a grammage of        approximately 100, 150 and 190 g/m² were prepared as in B), but        with 5% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from a ECF-bleached        Eucalyptus Globulus kraft pulp from Portugal) (C₁-C₃). The        characteristics of the microfibrillar cellulose were the        following: Fiber length: 0.41 mm (L&W Fiber Tester) and        stability:94% (sedimentation degree of a 0.5% pulp suspension;        water retention value (WRV): 6.8 g/g.    -   D) Single layer cellulosic products with a grammage of        approximately 100, 150 and 190 g/m² were prepared as in B), but        with 10% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from a ECF-bleached        Eucalyptus Globulus kraft pulp from Portugal) (D1-D3). The        characteristics of the microfibrillar cellulose were as in C).    -   E) Single layer cellulosic products with a grammage of        approximately 100, 150 and 190 g/m² were prepared as in A), but        with 5% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from a ECF-bleached        Eucalyptus Globulus kraft pulp from Portugal) (E1-E3). The        characteristics of the microfibrillar cellulose were as in C).    -   F) Single layer cellulosic products with a grammage of        approximately 100, 150 and 190 g/m² were prepared as in A), but        with 10% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from a ECF-bleached        Eucalyptus Globulus kraft pulp from Portugal) (F1-F3). The        characteristics of the microfibrillar cellulose were as in C).    -   G) A single layer cellulosic product with a grammage of        approximately 150 g/m² was prepared as in A), but with 3% (based        on the weight of cellulosic product) of 820 SL 80 (G1)    -   H) A single layer cellulosic product with a grammage of        approximately 150 g/m² was prepared as in G), but with addition        of 10% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from a ECF-bleached        Eucalyptus Globulus kraft pulp from Portugal) (H1). The        characteristics of the microfibrillar cellulose were as in C).    -   I) A single layer cellulosic product with a grammage of        approximately 150 g/m² was prepared as in G), but with addition        of 15% (based on the weight of celulosic product) microfibrillar        cellulose (prepared from a ECF-bleached Eucalyptus Globulus        kraft pulp from Portugal) (11). The characteristics of the        microfibrillar cellulose were as in C).    -   J) A single layer cellulosic product with a grammage of        approximately 150 g/m² was prepared as in A), but with addition        of 15% (based on the weight of cellulosic product)        microfibrillar cellulose (prepared from a ECF-bleached        Eucalyptus Globulus kraft pulp from Portugal) (J1). The        characteristics of the microfibrillar cellulose were as in C).

Single layer cellulosic products prepared according to A), B), C), D),E), F), G), H), I), and J) were analyzed for their grammage, density,tensile strength, burst strength, Z-strength, geometrical bendingresistance and porosity (see Table 11a-11d).

TABLE 11a A B Paper Property Unit 1 2 3 4 5 1 2 3 Grammage g/m² 102 145185 231 278 102 146 189 Density kg/m³ 463 484 467 484 481 339 320 345Tensile strength kN/m 3.90 5.42 6.51 7.66 9.61 2.9 3.92 5.28 TensileStiffness kN/m 445 589 670 740 888 335 406 515 Geom. Bending mN 15 41 84138 255 27 73 134 Resistance Bending Resistance Nm⁶/kg³ 13.3 13.0 12.410.6 11.2 24.9 22.4 18.9 Index Z-Strength kPa 376 505 454 469 410 307278 286 Burst strength kPa 230 361 463 598 662 177 236 318 BendtsenPorosity ml/min 1462 235 168 95 76 1575 800 400

TABLE 11b C D Paper Property Unit 1 2 3 1 2 3 Grammage g/m² 104 146 192105 149 197 Density kg/m³ 374 358 368 376 379 402 Tensile strength kN/m3.64 4.70 6.14 3.98 5.61 7.79 Tensile Stiffness kN/m 391 468 572 423 531680 Geom. Bending mN 24 70 138 23 62 149 Resistance Bending ResistanceNm⁶/kg³ 20.3 21.4 18.5 19.4 17.9 18.0 Index Z-Strength kPa 406 368 377521 494 486 Burst Strength kPa 243 342 424 288 399 570 Bendtsen Porosityml/min 762 302 260 410 232 145

TABLE 11c E F Paper Property Unit 1 2 3 1 2 3 Grammage g/m² 103 147 191105 151 194 Density kg/m³ 464 468 520 496 537 553 Tensile strength kN/m4.08 5.92 7.59 4.95 7.04 9.12 Tensile Stiffness kN/m 422 608 738 524 686838 Geom. Bending mN 14 47 83 16 39 76 Resistance Bending ResistanceNm⁶/kg³ 11.8 13.9 11.0 13.0 10.2 9.9 Index Z-Strength kPa 458 528 553514 564 596 Burst Strength kPa 283 439 608 354 507 708 Bendtsen Porosityml/min 712 175 85 136 140 51

TABLE 11d G H I J Paper Property Unit 1 1 1 1 Grammage g/m² 155 148 150154 Density kg/m³ 337 380 384 542 Tensile strength kN/m 4.05 5.74 6.417.63 Tensile Stiffness kN/m 411 551 582 724 Geom. Bending mN 86 73 70 39Resistance Bending Resistance Nm⁶/kg³ 25.7 21.7 20.4 10.0 IndexZ-Strength kPa 298 465 532 603 Burst Strength kPa 232 406 469 546Bendtsen Porosity ml/min 650 200 145 54

1-26. (canceled)
 27. A composition comprising microfibrillarpolysaccharide and thermoplastic microspheres, wherein the weight ratioof microfibrillar polysaccharide to thermoplastic microspheres rangesfrom about 1:100 to about 200:1, and wherein the specific surface area,as determined by adsorption of N₂ at 177 K according to the BET methodusing a Micromeritics ASAP 2010 instrument, of the microfibrillarpolysaccharide is from 3 to 10 m²/g.
 28. The composition according toclaim 27, wherein the composition is aqueous.
 29. A cellulosic productobtained by the process comprising the steps of (i) providing an aqueoussuspension of cellulosic fibers, (ii) adding microfibrillarpolysaccharide, (iii) adding thermoplastic microspheres, (iv) dewateringthe suspension and forming a cellulosic product, wherein the weightratio of microfibrillar polysaccharide to thermoplastic microspheresranges from about 1:100 to about 200:1, and wherein the specific surfacearea, as determined by adsorption of N₂ at 177 K according to the BETmethod using a Micromeritics ASAP 2010 instrument, of the microfibrillarpolysaccharide is from 3 to 10 m²/g.
 30. A cellulosic product comprisingmicrofibrillar polysaccharide and thermoplastic microspheres, whereinthe weight ratio of microfibrillar polysaccharide to thermoplasticmicrospheres ranges from about 1:100 to about 200:1, and wherein thespecific surface area, as determined by adsorption of N₂ at 177 Kaccording to the BET method using a Micromeritics ASAP 2010 instrument,of the microfibrillar polysaccharide is from 3 to 10 m²/g.
 31. Thecellulosic product according to claim 30, wherein the product is boardor paperboard.
 32. The cellulosic product according to claim 30 having agrammage ranging from about 90 to about 500 g/m².
 33. The cellulosicproduct according to claim 30, wherein the microfibrillar polysaccharideis derived from softwood and/or hardwood.
 34. The cellulosic productaccording to claim 30, wherein the cellulosic product containsmechanical, recycled and/or kraft pulp.
 35. The cellulosic productaccording to claim 30, wherein the product contains microfibrillarpolysaccharide in an amount from about 0.1 to about 50 wt % based on theweight of cellulosic product.
 36. The cellulosic product according toclaim 30, wherein the product contains thermoplastic microspheres in anamount from about 0.01 to about 10 wt % based on the weight ofcellulosic product.
 37. A single layer cellulosic product comprisingmicrofibrillar polysaccharide derived from softwood and/or hardwood, andthermoplastic microspheres, wherein the weight ratio of microfibrillarpolysaccharide to thermoplastic microspheres ranges from about 1:100 toabout 200:1, and wherein the specific surface area, as determined byadsorption of N₂ at 177 K according to the BET method using aMicromeritics ASAP 2010 instrument, of the microfibrillar polysaccharideis from 3 to 10 m²/g.
 38. The cellulosic product according to claim 37,wherein the product is board or paperboard.
 39. The cellulosic productaccording to claim 37 having a grammage ranging from about 90 to about500 g/m².
 40. The cellulosic product according to claim 37, wherein thecellulosic product contains mechanical, recycled and/or kraft pulp. 41.The cellulosic product according to claim 37, wherein the productcontains microfibrillar polysaccharide in an amount from about 0.1 toabout 50 wt % based on the weight of cellulosic product.
 42. Thecellulosic product according to claim 37, wherein the product containsthermoplastic microspheres in an amount from about 0.01 to about 10 wt %based on the weight of cellulosic product.
 43. A method for producing aliquid packaging board, folding box board, or liner by (i) providing anaqueous suspension of cellulosic fibers, (ii) adding microfibrillarpolysaccharide, (iii) adding thermoplastic microspheres, (iv) dewateringthe suspension and forming a cellulosic product, wherein the weightratio of microfibrillar polysaccharide to thermoplastic microspheresranges from about 1:100 to about 200:1, and wherein the final specificsurface area, as determined by adsorption of N₂ at 177 K according tothe BET method using a Micromeritics ASAP 2010 instrument, of themicrofibrillar polysaccharide is from 3 to 10 m²/g.